• •
应昕1,2(), 杜淼4(
), 潘鹏举2,3, 单国荣2,3(
)
收稿日期:
2024-06-14
修回日期:
2024-07-21
出版日期:
2024-07-25
通讯作者:
杜淼,单国荣
作者简介:
应昕(2000—),男,硕士研究生,yingxin@zju.edu.cn
Xin YING1,2(), Miao DU4(
), Pengju PAN2,3, Guorong SHAN2,3(
)
Received:
2024-06-14
Revised:
2024-07-21
Online:
2024-07-25
Contact:
Miao DU, Guorong SHAN
摘要:
聚硫氨酯作为一种高折射率光学树脂,具有优异的光学、热学和力学性能,被广泛应用于光电领域。研究了不同单体结构和单体官能团比对聚硫氨酯综合性能的影响,结果表明,聚硫氨酯的折射率和色散程度与其含硫量和芳环结构含量有较大的关系,调整官能团比可使高折射率聚硫氨酯的折射率从1.6848上升至1.6900。聚硫氨酯的热学性能和力学性能受到单体结构刚性、官能团度、交联网络均匀程度和反应程度多个方面影响。制备的大部分聚硫氨酯都可以很好地满足光学透镜、光学黏结剂等领域的要求。
中图分类号:
应昕, 杜淼, 潘鹏举, 单国荣. 高折射率聚硫氨酯的合成、结构与性能[J]. 化工学报, DOI: 10.11949/0438-1157.20240654.
Xin YING, Miao DU, Pengju PAN, Guorong SHAN. Synthesis, structure and properties of high refrective index polythiourethane[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240654.
Sample | PTU1 | PTU2 | PTU3 | PTU4 | PTU5 | PTU6 |
---|---|---|---|---|---|---|
Composition | BES-XDI | BES-TDI | BES-MDI | PETMP-XDI | PETMP-MDI | BMMD-XDI |
Sulf contant(wt%) | 29.48 | 30.66 | 25.16 | 14.80 | 12.94 | 25.87 |
Refractive index(589 nm) | 1.6560 | 1.6785 | 1.6862 | 1.5912 | 1.6261 | 1.6596 |
Abbe’s number | 31.31 | 25.53 | 23.90 | 34.44 | 24.81 | 32.25 |
Total transmittance(%) | 87.67±0.64 | 86.81±0.77 | 86.48±0.75 | 89.20±0.58 | 84.42±0.86 | 87.11±0.73 |
Haze(%) | 0.22±0.08 | 4.1±0.13 | 0.06±0.02 | 2.07±0.09 | 18.78±0.20 | 0.71±0.11 |
λUV(nm) | 290 | 320 | 313 | 285 | 317 | 282 |
Tg(°C)-DSC | 69.6 | 122.5 | 125.3 | 70.9 | 124.3 | 98.4 |
Tg(°C)-DMA | 96.6 | 122.4 | 140.7 | 99.1 | 80.7/134.7 | - |
FWHM(°C) | 14.4 | 31.8 | 23.2 | 11.6 | 46.4/29.3 | - |
Td5%(°C) | 280 | 262.1 | 268.6 | 290.6 | 279.6 | 282.9 |
Tdmax(°C) | 301.7 | 283.9 | 295.4 | 303.4 | 350.8 | 312.3 |
Tensile strength(MPa) | 104.74±9.32 | 50.31±4.01 | 79.57±4.12 | 94.46±9.52 | 79.74±1.58 | - |
Tensile strength at break(MPa) | 104.74±9.32 | 50.31±4.01 | 79.57±4.12 | 63.80±3.38 | 69.50±3.94 | - |
Tensile strain at break(%) | 10.04±1.54 | 4.78±1.37 | 13.07+2.91 | 16.55±2.27 | 27.86±3.29 | - |
Tensile yield strength(MPa) | - | - | - | 94.46±9.52 | 79.74±1.58 | - |
Tensile strain at yield(%) | - | - | - | 9.92±0.49 | 11.61±0.45 | - |
Pencil hardness | 2H | 2H | 2H | 2H | 2H | 3H |
Density(g·cm-3) | 1.3633 | 1.3783 | 1.3417 | 1.3958 | 1.3846 | 1.4230 |
Contact angle(°) | 94.87±2.28 | 94.02±5.34 | 92.35±3.47 | 94.52±1.18 | 77.24±1.69 | 83.95±0.69 |
表1 不同体系聚硫氨酯的组成、光学性能、热学性能与力学性能
Table 1 Composition, optical, thermal and mechanical properties of polythiourethane of different systems
Sample | PTU1 | PTU2 | PTU3 | PTU4 | PTU5 | PTU6 |
---|---|---|---|---|---|---|
Composition | BES-XDI | BES-TDI | BES-MDI | PETMP-XDI | PETMP-MDI | BMMD-XDI |
Sulf contant(wt%) | 29.48 | 30.66 | 25.16 | 14.80 | 12.94 | 25.87 |
Refractive index(589 nm) | 1.6560 | 1.6785 | 1.6862 | 1.5912 | 1.6261 | 1.6596 |
Abbe’s number | 31.31 | 25.53 | 23.90 | 34.44 | 24.81 | 32.25 |
Total transmittance(%) | 87.67±0.64 | 86.81±0.77 | 86.48±0.75 | 89.20±0.58 | 84.42±0.86 | 87.11±0.73 |
Haze(%) | 0.22±0.08 | 4.1±0.13 | 0.06±0.02 | 2.07±0.09 | 18.78±0.20 | 0.71±0.11 |
λUV(nm) | 290 | 320 | 313 | 285 | 317 | 282 |
Tg(°C)-DSC | 69.6 | 122.5 | 125.3 | 70.9 | 124.3 | 98.4 |
Tg(°C)-DMA | 96.6 | 122.4 | 140.7 | 99.1 | 80.7/134.7 | - |
FWHM(°C) | 14.4 | 31.8 | 23.2 | 11.6 | 46.4/29.3 | - |
Td5%(°C) | 280 | 262.1 | 268.6 | 290.6 | 279.6 | 282.9 |
Tdmax(°C) | 301.7 | 283.9 | 295.4 | 303.4 | 350.8 | 312.3 |
Tensile strength(MPa) | 104.74±9.32 | 50.31±4.01 | 79.57±4.12 | 94.46±9.52 | 79.74±1.58 | - |
Tensile strength at break(MPa) | 104.74±9.32 | 50.31±4.01 | 79.57±4.12 | 63.80±3.38 | 69.50±3.94 | - |
Tensile strain at break(%) | 10.04±1.54 | 4.78±1.37 | 13.07+2.91 | 16.55±2.27 | 27.86±3.29 | - |
Tensile yield strength(MPa) | - | - | - | 94.46±9.52 | 79.74±1.58 | - |
Tensile strain at yield(%) | - | - | - | 9.92±0.49 | 11.61±0.45 | - |
Pencil hardness | 2H | 2H | 2H | 2H | 2H | 3H |
Density(g·cm-3) | 1.3633 | 1.3783 | 1.3417 | 1.3958 | 1.3846 | 1.4230 |
Contact angle(°) | 94.87±2.28 | 94.02±5.34 | 92.35±3.47 | 94.52±1.18 | 77.24±1.69 | 83.95±0.69 |
Sample | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
---|---|---|---|---|---|---|---|---|---|
-SH/-NCO | 0.90 | 0.95 | 1.00 | 1.05 | 1.10 | 1.20 | 1.30 | 1.40 | 1.50 |
Refractive index(589 nm) | 1.6848 | 1.6859 | 1.6862 | 1.6871 | 1.6880 | 1.6886 | 1.6895 | 1.6898 | 1.6900 |
Abbe’s number | 23.48 | 23.48 | 23.90 | 23.95 | 24.00 | 24.35 | 24.05 | 24.41 | 24.46 |
Total transmittance(%) | 86.62±0.83 | 86.50±0.69 | 86.48±0.75 | 86.48±0.62 | 86.35±0.87 | 86.34±0.93 | 86.50±0.76 | 86.20±0.68 | 86.36±0.91 |
Haze(%) | 0.09±0.02 | 0.17±0.04 | 0.06±0.04 | 0.04±0.03 | 0.16±0.05 | 0.50±0.08 | 0.59±0.06 | 0.47±0.09 | 1.57±0.10 |
λUV(nm) | 313 | 313 | 313 | 312 | 312 | 311 | 311 | 311 | 311 |
Tg(°C)-DSC | 131.3 | 127.8 | 125.3 | 119.9 | 119.4 | 101.1 | 98.0 | 89.7 | 69.4 |
Tg(°C)-DMA | 153.3 | 147.2 | 139.5 | 131.9 | 129.1 | 116.6 | 107.2 | 102.3 | 89.7 |
FWHM(°C) | 33.5 | 38.7 | 36.0 | 30.0 | 28.5 | 23.3 | 19.7 | 17.5 | 19.1 |
Td5%(°C) | 266.3 | 268.6 | 268.6 | 268.0 | 271.8 | 270.5 | 269.2 | 269.0 | 266.2 |
Tdmax(°C) | 290.1 | 292.5 | 295.4 | 293.6 | 297.1 | 290.1 | 290.9 | 287.6 | 286.0 |
Tensile strength(MPa) | 60.31±3.25 | 72.06±3.42 | 79.57±4.12 | 77.73±5.18 | 73.28±4.72 | 72.12±2.21 | 68.69±3.35 | 67.48±3.72 | 37.48±3.80 |
Tensile strain at break(%) | 7.45±1.66 | 8.37±1.58 | 13.07±2.91 | 15.7±3.13 | 17.42±2.68 | 16.84±3.89 | 11.58±1.73 | 6.89±1.76 | 4.02±1.30 |
Pencil hardness | 2H | 2H | 2H | 2H | 2H | 2H | H | H | HB |
Density(g·cm-3) | 1.3356 | 1.3392 | 1.3417 | 1.3463 | 1.3497 | 1.3573 | 1.3625 | 1.3686 | 1.3715 |
Contact angle(°) | 91.60±2.15 | 100.03±1.76 | 92.35±3.47 | 95.34±1.38 | 98.17±1.24 | 93.94±2.91 | 90.95±1.79 | 101.39±1.21 | 97.30±1.41 |
表2 不同官能团比聚硫氨酯的组成、光学性能、热学性能与力学性能
Table 2 Composition, optical, thermal and mechanical properties of polythiourethane with different functional group ratios
Sample | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
---|---|---|---|---|---|---|---|---|---|
-SH/-NCO | 0.90 | 0.95 | 1.00 | 1.05 | 1.10 | 1.20 | 1.30 | 1.40 | 1.50 |
Refractive index(589 nm) | 1.6848 | 1.6859 | 1.6862 | 1.6871 | 1.6880 | 1.6886 | 1.6895 | 1.6898 | 1.6900 |
Abbe’s number | 23.48 | 23.48 | 23.90 | 23.95 | 24.00 | 24.35 | 24.05 | 24.41 | 24.46 |
Total transmittance(%) | 86.62±0.83 | 86.50±0.69 | 86.48±0.75 | 86.48±0.62 | 86.35±0.87 | 86.34±0.93 | 86.50±0.76 | 86.20±0.68 | 86.36±0.91 |
Haze(%) | 0.09±0.02 | 0.17±0.04 | 0.06±0.04 | 0.04±0.03 | 0.16±0.05 | 0.50±0.08 | 0.59±0.06 | 0.47±0.09 | 1.57±0.10 |
λUV(nm) | 313 | 313 | 313 | 312 | 312 | 311 | 311 | 311 | 311 |
Tg(°C)-DSC | 131.3 | 127.8 | 125.3 | 119.9 | 119.4 | 101.1 | 98.0 | 89.7 | 69.4 |
Tg(°C)-DMA | 153.3 | 147.2 | 139.5 | 131.9 | 129.1 | 116.6 | 107.2 | 102.3 | 89.7 |
FWHM(°C) | 33.5 | 38.7 | 36.0 | 30.0 | 28.5 | 23.3 | 19.7 | 17.5 | 19.1 |
Td5%(°C) | 266.3 | 268.6 | 268.6 | 268.0 | 271.8 | 270.5 | 269.2 | 269.0 | 266.2 |
Tdmax(°C) | 290.1 | 292.5 | 295.4 | 293.6 | 297.1 | 290.1 | 290.9 | 287.6 | 286.0 |
Tensile strength(MPa) | 60.31±3.25 | 72.06±3.42 | 79.57±4.12 | 77.73±5.18 | 73.28±4.72 | 72.12±2.21 | 68.69±3.35 | 67.48±3.72 | 37.48±3.80 |
Tensile strain at break(%) | 7.45±1.66 | 8.37±1.58 | 13.07±2.91 | 15.7±3.13 | 17.42±2.68 | 16.84±3.89 | 11.58±1.73 | 6.89±1.76 | 4.02±1.30 |
Pencil hardness | 2H | 2H | 2H | 2H | 2H | 2H | H | H | HB |
Density(g·cm-3) | 1.3356 | 1.3392 | 1.3417 | 1.3463 | 1.3497 | 1.3573 | 1.3625 | 1.3686 | 1.3715 |
Contact angle(°) | 91.60±2.15 | 100.03±1.76 | 92.35±3.47 | 95.34±1.38 | 98.17±1.24 | 93.94±2.91 | 90.95±1.79 | 101.39±1.21 | 97.30±1.41 |
图4 不同体系聚硫氨酯(a)和不同官能团比聚硫氨酯(b)的DSC 二次升温曲线
Fig.4 DSC secondary heating curves of polythiourethane (a) with different systems, (b) with different functional group ratios
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